Patent GB-409696-A (GB)
Title: Improvements in the manufacture and production of substances producing fluorescence and soluble in hydrocarbon oils
IPC: C10M159/14
Filed: 1932-08-29
Abstract: Catalytic hydrogenation.--Condensation products obtained by condensing olefines of purely aliphatic constitution which are liquid at ordinary temperature and substantially free from diolefines with between 20 and 70 per cent of polynuclear organic substances in which none of the nuclei is saturated with hydrogen, at an elevated temperature and in the presence of at least 20 per cent of the amount of olefines of condensing catalysts of the Friedel-Crafts type, with or without the presence, in addition to the catalyst, of halides of metals of the first and second groups of the periodic system, are treated with hydrogen in the presence of hydrogenation catalysts at elevated temperatures, e.g. at 50--250 DEG  C., preferably at 70--175 DEG  C., preferably under pressure, e.g. at 20 to 200 atmospheres, and preferably in solution in an inert solvent, e.g. benzines of high boiling point, middle oils or lubricating oils of any consistency. Suitable catalysts are copper, cobalt or nickel alone or in admixture with each other or with other substances or on carrier substances, e.g. carbon, kieselguhr or pumice, also oxides of metals of the second to the seventh groups of the periodic system, especially group VI, or halides of silver, copper, cadmium, titanium, tin, vanadium, molybdenum, tungsten, manganese, nickel or cobalt, or sulphides of the second to the eighth groups of the periodic system, especially those of group VI.  In examples: (1) the product of condensation of a cracking product from soft paraffin wax with naphthalene at 100 DEG C. in the presence of aluminium chloride is treated with hydrogen at 100 DEG  C. and 100 atmospheres pressure in the presence of a nickel catalyst precipitated on kieselguhr; (9) a condensation product of olefines obtained by the dehydration of higher alcohols with naphthalene, anthracene and carbazole is treated with hydrogen at 120 DEG  C. and 200 atmospheres pressure in the presence of a catalyst consisting of copper, nickel and cobalt precipitated on pumice. Hydrocarbon oil compositions.--The above condensation products, hydrogenated or not, may be added to hydrocarbon oils, i.e. heavy oils or middle oils or lubricating oils or liquid motor fuels, such as benzines, or other liquid hydrocarbon fractions, whether paraffinic or naphthenic, in order to produce fluorescence. Suitable proportions specified are 0.1--0.2 per cent in the case of products manufactured in the presence of condensing catalysts alone, and 0.2--1 per cent in the case of products manufactured in the presence of halides of metals of the first and second groups of the periodic system in addition to the catalysts.ALSO:Substances producing fluorescence and soluble in hydrocarbon oils (i.e. heavy oils or middle oils or lubricating oils or liquid motor fuels, such as benzines, or other liquid hydrocarbon fractions, whether paraffinic or naphthenic) are manufactured by condensing olefines of purely aliphatic constitution which are liquid at ordinary temperature and substantially free from diolefines with between 20 and 70 per cent of polynuclear organic substances in which none of the nuclei is saturated with hydrogen, at an elevated temperature and in the presence of at least 20 per cent of the amount of olefines of condensing catalysts of the Friedel-Crafts type.  Suitable polynuclear compounds are unsubstituted polynuclear aromatic hydrocarbons such as naphthalene, anthracene or phenanthrene, or polynuclear heterocyclic compounds such as carbazole.  Suitable olefines are the liquid products obtained by cracking, preferably in the vapour phase, paraffinic hydrocarbons such as hard or soft paraffin wax, petroleum, or oils entirely or mainly consisting of paraffinic hydrocarbons, or olefines obtained by dehydration of alcohols, e.g. of octodecyl alcohol.  The condensation is carried out at 70--250 DEG  C., preferably at 125--200 DEG  C., and preferably in the presence of an indifferent diluent, e.g. a benzine fraction or other oil boiling at 150--200 DEG  C., while cooling externally.  The condensing agent may be aluminium chloride, preferably in an amount between 20 and 50 per cent of the amount of olefines.  The products may be added to hydrocarbon oils, e.g. in an amount of 0.1--0.2 per cent.  Improved products are obtained by carrying out the condensation in the presence of halides of metals of the first and second groups of the periodic system, e.g. sodium chloride or bromide, potassium chloride, cupric chloride, mercuric chloride or calcium chloride, in addition to the condensing agent, which latter may be aluminium chloride preferably in an amount between 25 and 60 per cent of the amount of olefines.  From 0.2 to 1 per cent of these products may be added to oils.  The products are also improved by treating them with hydrogen in the presence of hydrogenation catalysts at elevated temperatures, e.g. at 50--250 DEG  C., preferably at 70--175 DEG  C., preferably under pressure, e.g. at 20 to 200 atmospheres, and preferably in solution in an inert solvent, e.g. benzines of high boiling point, middle oils or lubricating oils of any consistency.  Suitable catalysts are copper, cobalt or nickel alone or in admixture with each other or with other substances or on carrier substances, e.g. carbon, kieselguhr or pumice, also oxides of metals of the second to the seventh groups of the periodic system, especially group VI, or halides of silver, copper, cadmium, titanium, tin, vanadium, molybdenum, tungsten, manganese, nickel or cobalt, or sulphides of the second to the eighth groups of the periodic system, especially those of group VI.  In examples: (1) cracked petroleum, naphthalene, anthracene oil and carbazole are heated to 200 DEG  C. with aluminium chloride while stirring, the product is cooled, stirred with water freed from solid matter and heated to 150 DEG  C. under 2 mm. pressure, producing a small amount of first runnings and a residue of oil; (2) a product obtained by cracking hard paraffin wax is diluted with first runnings, e.g. those from (1), and heated to 125 DEG  C. with naphthalene and aluminium chloride, the product being worked up as in (1) to yield first runnings and a viscous residue; (3) a product obtained by cracking paraffin wax is diluted with a high boiling benzine fraction and mixed with naphthalene, and aluminium chloride is added in three portions, the mixture being maintained at 150 DEG  C. after the addition of the last portion and the product worked up as in (1); (4) a product obtained by cracking paraffin wax is diluted with first runnings, e.g. those from (1), and polymerized in the presence of aluminium chloride while introducing the cracking gases obtained in the cracking of paraffin wax; when the temperature reaches 100 DEG  C., naphthalene, anthracene and phenanthrene are added and the mixture heated to 150 DEG  C., the product being distilled at 150 DEG  C. under 1 mm. pressure; (5) an olefine fraction obtained by splitting soft paraffin wax at 520 DEG C. is condensed with naphthalene in the presence of aluminium chloride and sodium chloride at 150 DEG  C., the product is cooled and stirred with water, the sludge is removed and the product distilled at 150 DEG  C. under 2 mm. pressure, whereby a small amount of oil passes over and a paste remains; (6) a cracking product from crude paraffin wax is heated to 165 DEG  C. with naphthalene, anthracene oil and carbazole in the presence of aluminium chloride, sodium chloride, potassium bromide and cuprous chloride, and the product is worked up as in previous examples; (7) a mixture of olefines obtained by the dehydration of higher alcohols is condensed with naphthalene at 100 DEG  C. in the presence of aluminium chloride, the product is stirred with water, filtered, dried, subjected to after treatment with aluminium chloride and mercury chloride at 100 DEG  C., again treated with water, dried and distilled at 1 mm. pressure, a paste remaining above 200 DEG  C.; (8) the product of condensation of a cracking product from soft paraffin wax with naphthalene at 100 DEG  C. in the presence of aluminium chloride is treated with hydrogen at 100 DEG  C. and 100 atmospheres pressure in the presence of a nickel catalyst precipitated on kieselguhr; (9) a condensation product of olefines obtained by the dehydration of higher alcohols with naphthalene, anthracene and carbazole is treated with hydrogen at 120 DEG  C. and 200 atmospheres pressure in the presence of a catalyst consisting of copper, nickel and cobalt precipitated on pumice. Specifications 295,990, 323,100, 326,500, 327,746, [all in Class 2 (iii)], and 362,465 are referred to.  The Provisional Specifications are not restricted in respect of the amounts of polynuclear organic compounds and condensing agents employed.  In an additional example in the first Provisional Specification, equal quantities of naphthalene and an olefine fraction obtained by cracking soft paraffin wax are condensed in the presence of aluminium chloride at a temperature up to 180 DEG  C., the product being worked up as in Example (1) of the Complete Specification.